Influence of counter-anion on the coordination geometry of manganese(II) complexes with methyl-2-pyrazinecarboximidate ligand

Two new complexes of [Mn(2-MPyzCI)₂Cl₂].H²O (1) and [Mn(2-MPyzCI)₂(H₂O)₂](NO₃)₂ (2) were synthesized from the reaction of MnX₂.4H₂O (X=Cl^? and NO₃^?) with 2-cyanopyrazine in methanolic solution. The chelating methyl pyrazine-2-carboximidate (2-MPyzCI) ligand is formed via the methanolysis of 2-cyanopyrazine. Although coordination environment around manganes(II) ions is similar, but these complexes are different in geometrical position of 2-MPyzCI ligands. As both compounds are synthesized under the same reaction conditions, the only difference between these two complexes are counter ions and changing of geometrical position of ligands can be considered as a result of influence of the counter-anions on the molecular structures.     

Promotion of a quality standard for Porana sinensis Hemsl. based on the efficacy-oriented Effect-Constituent Index

Multicompound determination for the quality control of traditional Chinese medicine (TCM) may often be inadequate, since these compounds may not be associated with, or fully represent, the clinical effects of TCM. Moreover, the individual contributions of each constituent to the pharmacological effect are often not considered. In China, Porana sinensis is widely used as a substitute for Erycibe sources to treat joint pain and rheumatoid arthritis. The existing quality control methods for P. sinensis neither consider the individual contributions of various compounds nor control the actual quality associated with different clinical efficacies. In the present study, a novel efficacy-oriented approach, named the effect-constituent index (ECI), was established for P. sinensis. Analyses of the spectrum–effect relationship and components in rat plasma were conducted to systematically and scientifically select quality markers. Quantitative analysis of multicomponents via a single marker method was introduced to enhance the practical application value of the established ECI. The established ECI shows a good ability to distinguish and predict the bioeffect-based quality of P. sinensis. The present study also provides a reference for the establishment and application of ECI as a quality control method for TCMs.     

Assessing the nucleophilic character of 2-amino-4-arylthiazoles through coupling with 4,6-dinitrobenzofuroxan: Experimental and theoretical approaches based on structure-reactivity relationships

A kinetic study of the reactions of potentially bioactive 2-amino-4-arylthiazoles with highly reactive 4,6-dinitrobenzofuroxan (DNBF) is reported herein in acetonitrile solution. The complexation reaction was followed by recording the UV–vis spectra with time at λ_max = 482 nm. Electronic effects of substituents influencing the rate of reaction have been studied using structure-reactivity relationships. It is shown that the Hammett plot relative to the reaction of DNBF with 2-amino-4-(4-chlorophenyl)thiazole exhibit positive deviation from the log k₁ versus σ correlation, while it showed excellent linear correlation in terms of Yukawa–Tsuno equation. It has be noticed that the nonlinear Hammett plot observed for 2-amino-4-(4-chlorophenyl) thiazole is not attributed to a change in rate-determining step but is due to nature of electronic effect of substituent caused by the resonance of stabilization of substrates. The second-order rate constant (k₁) relating to the bond C–C and C-N forming step of the complexation processes of DNBF with 4-substituted-aminothiazoles and 2-amino-5-methyl-4-phenylthiazole, respectively, is fit into the linear relationship log k = s_N (N + E), thereby permitting the assessment of the nucleophilicity parameter (N) of the 2-amino-4-arylthiazoles of the range (4.90 < N < 6.85). 2-amino-4-arylthiazoles is subsequently ranked by positioning its reactivity on the general nucleophilicity scale developed recently by Mayr and coworkers (2003) leading an interesting and a direct comparison over a large domain of π-, σ -, and n-nucleophiles. The global electrophilicity/nucleophilicity reactivity indexes of the 2-amino-4-arylthiazoles have been investigated by means of a density functional theory (DFT) method. .     

AlGaN/GaN高电子迁移率器件外部边缘电容的物理模型

AlGaN/GaN HEMT外部边缘电容Cofd是由栅极垂直侧壁与二维电子气水平壁之间的电场构成的等效电容.本文基于保角映射法对Cofd进行物理建模,考虑沟道长度调制效应,研究外部偏置、阈值电压漂移和温度变化对Cofd的影响:随着漏源偏压从零开始增加,Cofd先保持不变再开始衰减,其衰减速率随栅源偏压的增加而减缓;AlGaN势垒层中施主杂质浓度的减小和Al组分的减小都可引起阈值电压的正向漂移,正向阈值漂移会加强沟道长度调制效应对Cofd的影响,导致Cofd呈线性衰减.在大漏极偏压工作情况下,Cofd对器件工作温度的变化更加敏感.     

Magnetoelectric effects in multiferroic Y-type hexaferrites Ba(0.3)Sr(1.7)CoxMg(2-x)Fe(12)O(22)

Y-type hexaferrites with tunable conical magnetic structures are promising single-phase multiferroics that exhibit large magnetoelectric effects. We have investigated the influence of Co substitution on the magnetoelectric properties in the Y-type hexaferrites Ba(0.3)Sr(1.7)CoxMg(2-x)Fe(12)O(22)(x = 0.0, 0.4, 1.0, 1.6). The spin-induced electric polarization can be reversed by applying a low magnetic field for all the samples. The magnetoelectric phase diagrams of BaBa(0.3)Sr(1.7)CoxMg(2-x)Fe(12)O(22) are obtained based on the measurements of magnetic field dependence of dielectric constant at selected temperatures. It is found that the substitution of Co ions can preserve the ferroelectric phase up to a higher temperature, and thus is beneficial for achieving single-phase multiferroics at room temperature.     

A Shell-by-Shell Approach for Synthesis of Mesoporous Multi-Shelled Hollow MOFs for Catalytic Applications

Over the past two decades, advanced materials with hollow interiors have received significant attention in materials research owing to their great application potential across a vast number of technological fields. Though with great difficulty, multi-shelled hollow metal–organic frameworks (MSHMs) have also been successfully synthesized in recent years. Herein, a rational shell-by-shell soft-templating protocol has been devised to fabricate highly uniform multi-shelled hollow cobalt-imidazole-based MOF (ZIF-67). For the first time, it has become possible to endow mesoporosity to this new type of functional material (i.e., mesoporous MOFs). When used as carrier materials in catalytic reactions, in principle, these mesoporous MSHMs with high surface area not only improve the dispersity of metal nanoparticles (NPs), but also efficiently facilitate the mass diffusion of the reactions, resulting in enhanced catalyst activity. Moreover, the obtained MSHMs/M nanocomposites serve as base-metal bifunctional catalysts for one-pot oxidation-Knoevenagel condensation cascade reaction, in which the MSHMs itself serves as a pristine active catalyst in addition to its role of catalyst support. The results demonstrate that excellent multifunctional catalysts can be achieved via preparing intrinsically microporous bulk MOFs into extrinsically mesoporous MSHMs which possess many structural merits that conventional bulk MOFs do not have.     

Optimal spectral phase control of femtosecond laser-induced up-conversion luminescence in Sm^3+:NaYF4 glass

The spectral phase of the femtosecond laser field is an important parameter that affects the up-conversion(UC)luminescence efficiency of dopant lanthanide ions.In this work,we report an experi-mental study on controlling the UC lmiiinescence efficiency in Sm^3+:NaYF4 glass by 800-nm femtosec-ond laser pulse shaping using spectral phase modulation.The optimal phase control strategy efficiently enhances or suppresses the UC luminescence intensity.Based on the laser-power dependence of the UC luminescence intensity and its comparison with the luminescence spectrum under direct 266-nm fem-tosecond lciser irradiation,we propose herein an excitation model combining non-resonant two-photon absorption with resonance-media ted three-photon absorption to explain the experimental observations.